JPH061633A - Blue colored infrared and ultraviolet absorbing glass - Google Patents

Abstract

PURPOSE:To obtain the subject glass holding a balance of heat ray absorbing property with ultraviolet absorbing property and keeping transparency and easily reinforced ability by formulating two or more kinds of a high reducing rate frit glass, a relatively high reducing ratio frit glass, Glaubers salt and carbon in a glass raw material. CONSTITUTION:The composition of the glass component is >=98wt.% in total of 68-73wt.% (hereafter, %) SiO2, 0.1-2,5% Al2O3, 7-11% CaO, 2-4.2% MgO, 12-16% Na2O, 0.5-3% K2O, 0.03-0.25 SO3, 0.4-0.8% Fe2O3, 0.1-0.7% CeO2 or the like (a part is omitted). A desired optical property is attained by skillfully combining and adequately using two or more kind of <=10% (in terms of silica sand) high reducing rate frit glass having 350-500% reducing rate, <=0-4% relatively high reducing rate frit glass having 230-350% reducing rate, <=0.5% (in terms of silica sand) Glaubers salt and <=1.0% carbon thereinto to make the reducing ratio in the glass 100-200%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention, in the manufacture of sheet glass, provides a colored glass with a stable and reliable high reduction rate, a relatively high transparency, a heat ray and ultraviolet ray absorbing ability, and an easily strengthening ability. Infrared UV-absorbing glass with a blue color tone that is rather systematic and has a rather bright blue color, and is highly livable and highly safe, and can also be lightweight. Of course, the present invention provides an infrared and ultraviolet absorbing glass having a blue color tone which is useful as a window glass for a vehicle and a window glass for an automobile.

[0002]

2. Description of the Related Art In recent years, in order to save energy such as reduction of cooling load, it is possible to improve the human and physical properties by adding multifunctional functions such as reflection and absorption of heat rays to the glass itself or the glass surface. The need for flat glass products that contribute to comfort is rapidly increasing.

Therefore, in addition to the conventional heat ray-absorbing glass, a glass in consideration of ultraviolet ray absorption has been further proposed. For example, JP-A-64-18938 discloses Fe ₂ O ₃ containing at least 0.45% by weight of iron. A continuous flow of molten glass having a temperature control of redox conditions during the melting operation to give at least 35% of iron in the ferrous state, expressed as FeO,
And soda-lime-silica flat glass in a continuous process, which comprises shaping the glass into a flat glass product by a shaping operation, wherein said flat glass has a light transmittance of at least 65% and an infrared transmittance of 15% or less. A method of manufacturing is disclosed, wherein the glass is provided with a total iron content of less than 0.65% expressed as Fe ₂ O ₃ or the product glass has a sulfur content of less than 0.02% expressed as SO _3. It is described that it is preferable that
At least 0.45% by weight of total iron expressed as Fe ₂ O ₃ , of which at least 50% has iron in the ferrous state expressed as FeO and less than 0.02% by weight of sulfur expressed as SO _3. Disclosed is a soda-lime-silica glass article having a light transmittance of 65% and a total solar infrared transmittance of 15% or less, wherein the glass article is based on weight.
66 to 75% of SiO _2, 12 to 20 percent of Na ₂ O, 7 ~12% of CaO, 0
~ 5% MgO, 0-4% Al ₂ O ₃ , 0-3% K ₂ O, 0
~ 1% Fe ₂ O ₃ and the sum of CeO ₂ , TiO ₂ , V ₂ O ₅ or MoO ₃
It is stated that those having a composition consisting essentially of 0 to 1.5% are preferred.

Further, for example, in Japanese Unexamined Patent Publication No. 64-65044, the raw material of soda lime glass contains SiO ₂ 50 to 75%, Al ₂ O ₃ 12 to
Disclosed is a colored glass obtained by mixing 2 to 100 parts by weight of lava composed of 15%, Fe ₂ O ₃ 6 to 14%, CaO 2 to 11%, and MgO ₂ to 5% with respect to 100 parts by weight of the raw material. raw material, for example _{SiO 2 70~73%, Na 2 O13~15} , CaO7~12%, MgO1~4.5
%, Al ₂ O _{3 1 to} 1.8%, and the lava and 1300 to 1500 °
To obtain a glass melt at _{C, K 2 O 0 ~0.5%} , TiO 2 0 ~2
%, MnO ₂ 0 ~0.2%, optionally comprise SO ₂ 0 to 0.01%, by the mixing ratio of lava melting in a reducing atmosphere, it is described that exhibits a color tone from yellowish green scissors dark green to black ing.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, in Japanese Patent Laid-Open No. 18938/1988, the SO ₃ component is
Since it is less than 0.02% by weight, it is difficult to obtain a desired infrared-ultraviolet-absorbing glass by a melting operation means in the production of a flat glass by a normal float method, and various complicated means steps such as a liquefaction step and a melting step. , A clarification stage, a stirring chamber, a stirrer, etc. are required, and the one disclosed in JP-A-64-65044 is a glass composition which is a sufficiently easily strengthened glass composition and homogeneity is important. , And it is not always said that it is suitable for its production, and it is not always said that it can express the desired blue color tone sufficiently stably.

[0006]

The present invention has been made in view of such drawbacks of the prior art, and is based on an easily tempered glass component composition containing a coloring component composition and a functional optical characteristic component composition, and The reduction rate in the glass is controlled to fall within a specific range by using the above specified high reduction rate and / or relatively high reduction rate frit glass, the specified Glauber's salt and the specified carbon in a glass raw material batch in an appropriate combination. By doing so, the coefficient of thermal expansion, Young's modulus and Poisson's ratio are made larger and the thermal conductivity is made smaller, and at least the desired heat ray absorption and ultraviolet absorption characteristics, etc. are obtained. It has the relatively blue color tone of the above-mentioned expected relatively blue-like color tone, and also has sufficient weather resistance and moldability. There is provided an infrared ultraviolet absorbing glass of blue color tone suitable for plate glass and easily reinforcing the.

That is, the present invention is expressed in% by weight,
Substantially SiO₂68-73%, Al₂O₃ 0.1 to 2.5%, CaO 7 to 1
1%, MgO2-4.2%, Na₂O12-16%, K₂O 0.5 ~ 3
%, SO ₃0.03 to 0.25%, Fe₂O₃0.4-0.8%, CeO₂ 0.1 ~
0.7% and Ti0₂, MnO, ZnO, CoO, etc.
%, The sum of these is 98% or more, and SiO₂
＋ Al₂O₃ 69-74%, CaO + Mg0 11-15%, Na₂O + K₂O 13
~ 17% glass composition
At least 10% high reduction rate frit glass / silica sand
Reduction rate (Fe²⁺/ Fe³⁺) High reduction rate of 350-500%
Lit glass, relatively high reduction rate frit glass / silica sand
Reduction rate of 4-0% (Fe²⁺/ Fe³⁺) 230-350% relatively
High reduction rate frit glass, Glauber's salt / Quartz with 0.5% or less of sand
Silica and carbon / silver with less than 1.0% carbon / silica sand
The reduction ratio of the glass (Fe
²⁺/ Fe³⁺) Is 100-200%
Infrared UV absorbing glass with a blue tone.

In the glass raw material batch, at least the high reduction rate frit glass / silica sand having a high reduction rate frit glass of 1 to 8%, the mirabilite / silica sand of 0.4% or less, and the mirabilite and carbon / silica sand of 0.5% or less. 2. A combination of two or more of the carbons of claim 1 is used to replenish the iron content in the glass raw material batch by using a valve stem (Fe ₂ O ₃ ) and / or a relatively high reduction rate frit glass. Infrared ultraviolet absorbing glass having a blue color tone according to 1.

In addition, the Fe ₂ O ₃ component in the high-reduction-ratio frit glass is 0.1 to 1.0% in terms of weight%, and the above infrared ray ultraviolet absorbing glass having a blue color tone.

Further, the above-mentioned blue-tone infrared-ray absorbing glass is characterized in that the MnO component in the blue-tone infrared-ray absorbing glass is 10 to 350 ppm.
Furthermore, the optical characteristics of the infrared-ray-absorbing glass of the blue color tone described above have a visible light transmittance of 60% at a plate thickness of 5 mm.
As described above, the solar radiation transmittance is 50% or less, the ultraviolet ray transmittance is 25% or less, the transmittance at a wavelength of 1100 mm is 5 to 11%, the main wavelength by the light source A is 495 to 505 nm, and the stimulus purity is 5 to 9. Each of the above-mentioned infrared-ray and ultraviolet-absorbing glasses having a blue color tone is provided.

In the blue heat ray absorbing glass, the SiO ₂ component is set to 68 to 73% by weight. When it is less than 68%, the surface is liable to be burned and the weather resistance is lowered to cause practical problems. are those that arise, greater than 73% when the easy-reinforcing decreases its, which melting becomes difficult, Al ₂ O ₃
The content of 0.1 to 2.5% by weight means that if it is less than 1%, the weather resistance and durability are lowered and the surface is liable to cause burns and the like, which causes practical problems. Devitrification is likely to occur, the molding temperature range is narrowed, manufacturing is difficult, and long-term stability is difficult to secure. However, it may be about 0.1% when the humidity is not high. The CaO content of 7 to 11% by weight means that if it is less than 7%, the easy strengthening property will be deteriorated, the flux will be insufficient, and the melting temperature will be high, and the flow temperature will not be lowered, making it difficult to manufacture. If it exceeds 11%, devitrification is likely to occur, and the molding work range is narrowed, making it difficult to manufacture. The reason why the content of MgO component is 2 to 4.2% is that the melting temperature rises when the content is less than 2% and the operation is difficult. Since the range is narrowed, it becomes difficult to manufacture, 4.
If it exceeds 2%, the easiness of strengthening decreases.

Further, the reason why the Na ₂ O component is set to 12 to 16% by weight is that when it is less than 12%, the easy strengthening property is lowered, the moldability becomes difficult, and devitrification easily occurs, so that the operating range is narrowed and the production is reduced. If it exceeds 16%, the weather resistance will decrease, and the surface will be liable to be burned, causing practical problems. The K ₂ O content of 0.5 to 3% was is 0.
If it is less than 5%, the toughness is lowered, and if it exceeds 3%, the weather resistance is lowered and the cost is also high.The SO ₃ component is 0.03 to 0.25% by weight. It can only be made to the extent that defoaming or inhomogeneity tends to be inadequate in the melting of, and is preferably 0.04% or more, and when it exceeds 0.25%, it particularly affects the coloring state of glass, such as yellow or amber. It is because it is easy to shift to the desired color tone and the desired blue color tone, if anything a vivid blue color tone cannot be obtained, preferably around 0.15% and even more within the range. The lower part is good.

Further, the SiO ₂ + Al ₂ O ₃ is contained in a weight percentage of 69 to
The reason why 74% is set is that if it is less than 69%, the weather resistance is deteriorated, and if it exceeds 74%, the easily strengthening property is deteriorated.
The weight percentage of O + MgO is set to 11 to 15% because CaO and MgO components are used for lowering the melting temperature, and if less than 11%, the easy strengthening property decreases, and if it exceeds 15%, devitrification tends to occur. It is difficult to manufacture, and Na ₂ O + K ₂
The percentage of O is set to 13 to 17% because if it is less than 13%, the easy strengthening property will decrease, devitrification will occur easily, the working temperature range will be narrow in molding, and the manufacturing will become difficult. The cost is high and the cost is high.

Fe₂O₃0.4-0.8% by weight of ingredients
And the reduction rate of the glass (Fe²⁺/ Fe ³⁺) Is 100-200%
Is the amount of FeO component that absorbs infrared rays and UV
Fe that absorbs the rays and more reliably secures the desired blue color tone₂O
₃Stabilizes the various optical characteristics described above as the total amount of the components
It is necessary to work with the above reduction rate because
If it is less than 0.4%, the effect against the above is inferior.
If it exceeds, the blue color tone tends to be dark and dark, especially visible
It is not preferable because the light transmittance is inferior.
And preferably Fe₂O₃About 0.45-0.75% as component concentration
And the reduction rate is about 110-170%.

Further, CeO ₂ 0.1-0.7% is defined as Ce
It is a range in which the ultraviolet absorbing effect of O ₂ is effectively used, and if it is limited to only ultraviolet rays, it is more effective to have a higher CeO ₂ concentration, but CeO ₂ is an oxidizing raw material and if it is used in large amounts, the reducing property of the batch will be reduced. It also lowers the absorption of FeO in the infrared region. While keeping the relatively high reduction rate almost unchanged, the valence of Ce in the glass is Ce ⁴⁺ or Ce ³⁺ .
Almost colorless Ce ³⁺ is mainly used, and together with the above-mentioned reducing agent, the ratio of Fe ₂ O ₃ and FeO in total iron is controlled so that both the absorption in the ultraviolet region and the absorption in the infrared region are effective. It is within the above range. The concentrations of the Fe ₂ O ₃ component and the CeO ₂ component are preferably approximately the same.

Further, other trace components such as TiO ₂ , MnO, ZnO and CoO are 1 to 0%, preferably 0.5% or less, and at least one of these components may be contained. .

Further, regarding the MnO component, for example,
The relationship between Fe and Mn tends to oxidize Fe and the reduction rate tends to be low, although a small amount, and the relationship between Ce and Mn tends to oxidize Mn, which does not affect the reduction rate. Since it is almost absent, Mn interacts with Fe and Ce and others in a neutral manner, and MnO around 500 nm is present.
It is possible to adjust the color tone with a slight absorption force without affecting the color tone, and if a large amount of MnO component is used, the phenomenon such as solarization tends to occur. , Preferably about 350 ppm or less. It is preferably about 50 to 250 ppm.

Further, regarding the CoO component, for example, 0 to
It is about 10 ppm, preferably about 1 to 5 ppm.
The CoO component is added only for adjusting the blueness of the blue color tone, and may be contained as an impurity in a trace amount.

Furthermore, regarding the ZnO component, for example, when a sulfate (eg, Glauber's salt) is melted under the condition of strong reduction, a sulfide (in the case of iron, Fe ³⁺ and S ^{2 —} are combined). ,
Polysulfide is formed and sometimes produces a yellowish brown coloring called carbon amber.However, it easily binds with S ^2- and forms a compound that is colorless at the same time, which adversely affects the coloring. The carbon amber can be prevented from being colored without generating a sulfide that gives It is preferably about 0.1% or less, more preferably 0.05% or less.

It is needless to say that a trace amount of impurity components may be contained as an optional component from the raw material used or cullet, and this amount does not cause any particular problem.

Next, the reduction ratio (Fe ²⁺ / Fe ³⁺ ) is from 350 to
The high reduction rate frit glass, which is 500%, utilizes its high reducing ability, and when it is used to produce infrared and ultraviolet absorbing glass with a blue color tone, the reduction rate is stably maintained, the furnace and the molten state are kept stable. This is because it is necessary to improve stability, to homogenize the glass and to ensure the homogeneity of the blue color tone, and the addition amount is 10% or less, preferably 1 to 8 when the ratio of silica sand in the raw material batch is 100. %, More preferably 2
It is about 6%. Further, the iron content in the high reduction rate frit glass is about 0.1 to 1.0%. The other component composition is not particularly limited as long as it does not contain a coloring component such as CoO, Se, and Cr, but is procured separately, for example.
SiO ₂ -Al ₂ O ₃ -C including Fe ₂ O ₃ , FeO, MnO, SO ₃ , S ^2-, etc.
Examples thereof include aO-MgO glass composition.

Furthermore, the reduction ratio (Fe ²⁺ / Fe ³⁺ ) is
Regarding the relatively high reduction rate frit glass of 230 to 350%, although it is used in place of red iron oxide, it has the same action and effect as the high reduction rate frit glass, and especially FeO.
It contains a relatively large amount of components, such as SiO ₂ -Al ₂ O ₃ -FeO-Fe ₂ containing separately procured MgO, MnO, SO _3, etc.
It is an O ₃ -CaO glass composition. The amount of addition is 4 to 0%, preferably 3 to 0% with respect to silica sand.

Among them, frit glass with a high reduction rate of at least 10% or less (Fe ²⁺ / Fe ³⁺ ) in the glass raw material batch, a high reduction rate frit glass of 350 to 500%, and a relatively high reduction rate. Reducing rate of frit glass / silica sand of 4 to 0% (Fe ²⁺ / Fe ³⁺ ) 230 to 350% of relatively high reducing rate frit glass, mirabilite of mirabilite / silica of 0.5% or less and carbon / silica sand of 1.0 %, The reduction rate of the glass (Fe ²⁺ / Fe ³⁺ )
The was a 100 to 200% is, FeO in the glass frit of the respective, it is desirable to merely increase the high reduction ratio can be a Fe ₂ O ₃ component concentration, in the usual tank furnace normal furnace operation Within the range, defoaming or homogeneity is secured, and the amount of FeO component that absorbs infrared rays is balanced with the amount of Fe ₂ O ₃ component that absorbs ultraviolet rays and secures the desired blue color tone. The above-mentioned various optical characteristics can be stably obtained, and high yield can be obtained without causing defects such as uneven color and uneven base.
This is because it is possible to stably produce the infrared-ray absorbing glass having a blue color tone of the present invention with high quality and high efficiency. It should be noted that mirabilite / silica sand is preferably 0.4% or less and carbon / silica sand is 0.5% or less.

Further, the optical characteristics of the infrared ray absorbing glass of the blue color tone are as follows: visible light transmittance of 60% or more, solar radiation transmittance of 50% or less, ultraviolet transmittance of 25% or less at a plate thickness of 5 mm. The transmittance at a wavelength of 1100 mm is 5 to 11%, the main wavelength by the light source A is 495 to 505 nm, and the stimulus purity is 5 to 9 because sufficient transparency is ensured, there is no glare, and safety is high. This is because the air-conditioning effect is also enhanced, the living property is high, the property is friendly to humans and the environment, and it is useful not only for construction but also for window materials for automobiles.

The blue-tone infrared and ultraviolet absorbing glass of the present invention is an easily tempered glass composition, and is a thin glass sheet having a thickness of about 1 mm to a thick glass sheet having a thickness of about 10 mm. Those having increased strength, semi-strengthened, reinforced, etc. are useful for use in single-plate glass, laminated glass, laminated glass or double-glazing, etc., and are particularly useful for vehicle window glass.

[0026]

As described above, the infrared-ray ultraviolet absorbing glass having a blue color tone of the present invention is based on the easily tempered glass component composition containing the coloring component composition and the functional optical characteristic component composition, and is contained in the glass raw material batch as specified above. Reduction rate frit glass or / and comparatively high reduction rate frit glass, specified Glauber's salt and specified carbon are used in an appropriate combination of at least two types to control the reduction rate in the glass within a specific range. Therefore, considering the melting property, clarification property, weather resistance, moldability, devitrification property, cost, etc., the manufacturing conditions and the properties of the glass in a conventional glass melting furnace can be controlled at a considerably high reduction rate. Do not change and make the coefficient of thermal expansion, Young's modulus and Poisson's ratio larger and the coefficient of thermal conductivity smaller. Both of them have at least sufficient heat ray absorption characteristics and ultraviolet ray absorption characteristics, etc., and have excellent transparency for object identification, no glare, and high safety can be secured. It develops a color tone that includes a relatively blueish blue color, and is well harmonized with, for example, cars and the interior and exterior, and is environmentally friendly and excellent, and furthermore, it cannot be obtained by the conventional heat strengthening method. It is easy to obtain a sufficient degree of strengthening or sufficient strength even for thin colored glass, etc., and of course, it is suitable for building glass of blue color tone suitable for plate glass and having sufficient temperability, weather resistance, and moldability. Provided is an infrared and ultraviolet absorbing glass having a blue color tone which is useful for furniture glass, cooking glass, especially window glass for vehicles such as automobiles.

[0027]

EXAMPLES Examples of the present invention will be described below. Example 1 As a glass raw material, for example, silica sand, feldspar, soda ash, dolomite, limestone, mirabilite, red iron oxide, titanium oxide, cerium carbonate or ilmenite, carbon, and zinc oxide, further reduction ratio (Fe ²⁺ / Fe ³⁺ ) 350-500%
The high reduction rate frit glass, etc. is appropriately selected and used. Especially, the high reduction rate frit glass / silica sand is about 6%, mirabilite / silica sand is about 0.3%, and carbon / silica sand is about 0.2%. The glass component composition of (1) is weighed and blended as a target composition, and the furnace is operated in a range that can be usually adjusted by a normal plate glass melting kiln, while melting, homogenizing and clarifying while sufficiently ensuring the high reduction rate, and molding. A plate glass was obtained.

The above 350 to 500% (for example, about 485%
The high reduction rate frit glass is about Fe ₂ O
SiO ₂ -Al ₂ O ₃ -CaO-M including ₃ , FeO, MnO, SO ₃ , S ^2-, etc.
It is a gO-based glass composition. In addition, the amount of cullet used is approximately 20% in the raw material batch of normal float clear glass.
Used to some extent.

[0029] For the plate glass, it was confirmed by a wet analysis method or the like based on JIS R-3101, about the weight display, SiO ₂ 7
0.4%, Al ₂ O ₃ 1.9%, CaO 9.0%, MgO 3.5%, Na ₂ O 13.3
%, K ₂ O 0.9%, Fe ₂ O ₃ 0.44%, CeO ₂ 0.42%, SO ₃ 0.07
%, MnO is about 250ppm, and the sum of the components is 99.93.
% And SiO ₂ + Al ₂ O ₃ 72.3%, CaO + MgO 12.5
%, An _{Na 2 O + K 2 O14.2%} , the reduction ratio (Fe ²⁺ / Fe ³⁺⁾ became approximately 111%.

The glass has a viscosity temperature of about 10 ⁹ poise.
650-685 ℃, 10 ¹² poise is 555-585 ℃, and the temperature difference between the two is about 96-103 ℃ is a glass composition, the thickness is about 3.8 mm, size 50 mm × 50 mm
As a glass plate of No. 3, each sample of infrared-ray-absorbing glass of blue color was used.

With respect to this sample, visible light transmittance (%), ultraviolet transmittance (%), solar radiation transmittance (%) and dominant wavelength (nm) as optical characteristics were measured with a light source A in a plate glass having a thickness of 5 mm. 340 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) and JIS Z-8722, JIS R-31
06, measured and calculated according to ISO / DIS-9050.

As a result, the infrared ray-absorbing glass of blue color tone has a visible light transmittance of about 72.8%.
Solar transmittance is about 42.4%, dominant wavelength is about 500-501,
The transmittance in the infrared region (around 1100 nm) is about 10%, the ultraviolet transmittance is about 20%, and the stimulation purity is about 6.
It was a glass having a desired blue-based color tone and infrared and ultraviolet absorption performance.

Further, regarding the easy strengthening property, it was confirmed that the above-mentioned glass had the above-mentioned viscous temperature and cleared a predetermined specific range, and the above-mentioned sample was heated at an ambient temperature of about 650 to 730 ° C. After heating for about 5 minutes in the furnace, normal tempering is performed to obtain a tempered glass plate, and the glass plate is JI
When examined according to S R-3211, it was an infrared-ultraviolet absorbing glass having a blue color tone with high efficiency and high yield even on a thin glass plate, and which was highly easily toughened and sufficiently satisfied the specified standard.

Example 2 The same glass raw material and raw material batch as in Example 1 were used, and only the value of Glauber's salt / silica sand was changed to 0.2%, and the glass was blended so as to obtain the desired infrared ray ultraviolet absorbing glass of a blue color tone. The composition was calculated, weighed and blended, melted, etc., and the obtained glass was similarly sampled.

The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1 above. As a result, the glass component composition was SiO ₂
The basic composition is almost the same, and the different composition is SO ₃ about 0.05% by weight, ZnO 0.01, MnO about 250p.
It is around pm, the total sum of the components is 99.82%, SiO ₂ +
Al ₂ O ₃ 72%, CaO + MgO 13.0%, Na ₂ O + K ₂ O 14.0%, and the reduction rate was around 137%. The optical characteristics are visible light transmittance of about 71.6%, solar radiation transmittance of about 40.3%, dominant wavelength of about 499 to 500 nm, infrared region (around 1100 nm).
Transmittance is about 7-8%, and UV transmittance is about 2
It was about 1.1 to 20.2%, the stimulating purity was about 6 to 7, and it was the expected blue-tone infrared and ultraviolet absorbing glass.

Further, regarding the easy strengthening property, the above-mentioned Example 1 was used.
When the same procedure as in Example 1 was performed, it was possible to obtain a product that sufficiently satisfied the standards determined by JIS and passed the above standards even with a thin glass plate with high efficiency and high yield. It was.

Example 3 Using the same glass raw material and raw material batch as in Example 1, the value of Example 1 and the high reduction rate frit glass / silica sand was changed to 8%, and the value of mirabilite / silica sand was changed to 0.2%. It is only necessary to calculate the glass composition and weigh and mix it so that it will be the desired infrared and ultraviolet absorbing glass with a blue color tone, melting operation,
Molding and the like were performed, and the obtained glass was similarly sampled.

The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1 above. As a result, the glass component composition was SiO ₂
The basic composition is almost the same, but the different composition is about 0.05% by weight of SO ₃ and about 290 ppm of MnO, the total of the components is 99.86%, and SiO ₂ + Al ₂ O ₃ 72
%, CaO + MgO 12.5%, Na ₂ O + K ₂ O 14.2%, and the reduction rate was around 149%. The optical characteristics are visible light transmittance of about 69.1%, solar radiation transmittance of about 37.5%, dominant wavelength of about 500 to 501 nm, transmittance of about 5 to 6% in the infrared region (around 1100 nm), and ultraviolet light. Transmittance of about 19.5 to 20.2
%, The irritation purity was about 6 to 7, and it was the desired infrared absorption glass with a blue color tone.

Further, regarding the easy strengthening property, the above-mentioned Example 1 was used.
When the same procedure as in Example 1 was performed, it was possible to obtain a product that sufficiently satisfied the standards determined by JIS and passed the above standards even with a thin glass plate with high efficiency and high yield. It was.

Example 4 The same glass raw materials and raw material batches as in Example 1 were used, and the red iron oxide of Example 1 was used instead of red iron oxide, and the reduction ratio was 230 to 35.
Relatively high reduction rate frit glass of 0% is about 2.
Using 7%, the glass composition was calculated and weighed and compounded so as to obtain the desired infrared ray ultraviolet absorbing glass having a blue color tone, and the melting operation, molding, etc. were performed, and the obtained glass was similarly sampled.

The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1 above. As a result, the glass component composition was SiO ₂
The basic composition is almost the same, but the different composition is about 0.04% SO ₃ and about 250 ppm MnO in weight, and the sum of the components is 99.86%, and SiO ₂ + Al ₂ O ₃ 72
%, CaO + MgO 12.5%, Na ₂ O + K ₂ O 14.2%, and the reduction rate was around 140%. The optical characteristics are visible light transmittance of about 70.5%, solar transmittance of about 38.8%, dominant wavelength of about 500 to 501 nm, transmittance of about 6 to 7% in the infrared region (around 1100 nm), and ultraviolet light. Transmittance of about 19.9 to 20.7
%, The irritation purity was about 6 to 7, and it was the desired infrared absorption glass with a blue color tone.

Further, as to the easy strengthening property, the above-mentioned Example 1 was used.
When the same procedure as in Example 1 was performed, it was possible to obtain a product that sufficiently satisfied the standards determined by JIS and passed the above standards even with a thin glass plate with high efficiency and high yield. It was.

The above 230-350% (for example, about 280%)
The frit glass with a relatively high reduction rate of (about) is a SiO ₂ -Al ₂ O ₃ -FeO-Fe ₂ O ₃ -C containing separately procured MgO, MnO, SO _3, etc.
It is an aO-based glass composition.

Example 5 Using the same glass raw material and raw material batch as in Example 1, the value of Example 1 and the high reduction rate frit glass / silica sand was 8%, and the value of Glauber's salt / silica sand was 0.5%. In place of red iron oxide of Example 1, a relatively high reduction rate frit glass having a reduction rate of 230 to 350% was used in an amount of about 2.8% with respect to silica sand, and the glass composition was adjusted so as to obtain the desired infrared ray ultraviolet absorbing glass of a blue color tone. The glass obtained was calculated, weighed and blended, melted, molded and the like, and the obtained glass was similarly sampled.

The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1 above. As a result, the glass component composition was SiO ₂
The basic composition is almost the same, but the different composition is about 0.04% SO ₃ and about 290 ppm MnO by weight, the sum of the components is 99.86%, and SiO ₂ + Al ₂ O ₃ 72
%, CaO + MgO 12.5%, Na ₂ O + K ₂ O 14.2%, and the reduction rate was around 136%. The optical characteristics are visible light transmittance of about 71%, solar radiation transmittance of about 39.8%, dominant wavelength of about 500 to 501 nm, and solar radiation transmittance of about 7 to 8% in the infrared region (around 1100 nm). , UV transmittance is about 19.9
Approximately 20.4%, stimulating purity was approximately 6-7, and it was the expected infrared absorption glass of blueish color.

Further, regarding the easy strengthening property, the above-mentioned Example 1 was used.
When the same procedure as in Example 1 was performed, it was possible to obtain a product that sufficiently satisfied the standards determined by JIS and passed the above standards even with a thin glass plate with high efficiency and high yield. It was.

As the cullet, for example, an appropriate amount of cullet such as blue can be used as appropriate, and the above-described embodiments are examples of the present invention, and the present invention is not limited to these embodiments.

[0048]

According to the present invention, the specific oxide component consisting of the basic component composition and the coloring or functional optical property imparting component composition is made into a specific composition range, and in particular, a high reduction rate frit glass, and a relatively high content. Reduction rate It is possible to control the reduction rate in glass by skillfully combining two or more of frit glass, mirabilite and carbon, and by using an appropriate amount, it is possible to suppress a reduction in reduction rate and maintain a considerably high reduction rate. , Which has heat ray absorption characteristics and ultraviolet ray absorption characteristics in a well-balanced manner, has sufficient transparency, retains easy tempering properties, and has the desired blue color tone. The glass can be manufactured in a sufficiently stable manner without any change to, and the glass has high habitability, high safety, high environmental performance in terms of both human and physical properties, and can be made lighter. so Become a shall, architectural window glass or the like, of course, is to provide a blue color infrared ultraviolet absorbing glass to be useful when applied to a window glass for automobiles.

Claims (5)

[Claims] 1. Substantially SiO, expressed in% by weight.₂68-73
%, Al₂O₃ 0.1 to 2.5%, CaO 7 to 11%, MgO 2 to 4.2
%, Na₂O12-16%, K₂O 0.5-3%, SO₃0.03 to 0.25
%, Fe₂O₃0.4-0.8%, CeO₂ 0.1-0.7% and Ti
0₂, MnO, ZnO, CoO, etc.
Is 98% or more, and SiO₂＋ Al ₂O₃ 69-74%,
CaO + Mg0 11-15%, Na₂O + K₂O 13 to 17% glass component
Composition, and at least high in the glass raw material batch
Reduction rate Reduction rate of frit glass / silica sand of 10% or less (Fe²⁺
/ Fe³⁺) 350-500% high reduction rate frit glass, comparison
High reduction rate Frit glass / silica sand 4 to 0% reduction rate
(Fe²⁺/ Fe³⁺) Relatively high reduction frit of 230-350%
Glass, Glauber's salt / Glauber's salt with 0.5% or less of Glauber's sand
Of carbon with less than 1.0% of silica / silica sand
Used together, the reduction rate of the glass (Fe²⁺/ Fe³⁺) Is 100
~ 200% blue tones characterized by
Infrared UV absorbing glass. 2. The high-reduction-rate frit glass having at least 1 to 8% of high-reduction-rate frit glass / silica sand, the mirabilite having 0.4% or less of mirabilite / silica and 0.5% or less of carbon / silica in the glass raw material batch. 2. A combination of two or more of the carbons of claim 1 is used to replenish the iron content in the glass raw material batch by using a valve stem (Fe ₂ O ₃ ) and / or a relatively high reduction rate frit glass. Infrared ultraviolet absorbing glass having a blue color tone according to 1. 3. Fe ₂ O ₃ in the high reduction frit glass
The infrared ray absorbing glass having a blue color tone according to claim 1 or 2, wherein the content of the component is 0.1 to 1.0% by weight. 4. The infrared-ray absorbing glass of blue color tone according to claim 1, wherein the MnO component in the infrared-ray absorbing glass of blue color tone is 10 to 350 ppm. 5. The optical characteristic of the infrared-ray ultraviolet absorbing glass having a blue color tone is that the visible light transmittance is 60 at a plate thickness of 5 mm.
% Or more, solar radiation transmittance is 50% or less, ultraviolet ray transmittance is 25% or less, transmittance at a wavelength of 1100 mm is 5 to 11%, main wavelength of light source A is 495 to 505 nm, and stimulus purity is 5 to 9 An infrared and ultraviolet absorbing glass having a blue color tone according to claim 1.